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1.

Вид документа : Статья из журнала
Шифр издания : 53/S 34
Автор(ы) : Schmelzer J. W. P., Boltachev G. Sh., Baidakov V. G.
Заглавие : Classical and generalized Gibbs' approaches and the work of critical cluster formation in nucleation theory
Место публикации : Journal of Chemical Physics. - 2006. - Vol. 124, № 19. - С. 194503/1-194503/18
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): clusters
Аннотация: In the theoretical interpretation of the kinetics of first-order phase transitions, thermodynamic concepts developed long ago by Gibbs are widely employed giving some basic qualitative insights into these processes. However, from a quantitative point of view, the results of such analysis, based on the classical Gibbs approach and involving in addition the capillarity approximation, are often not satisfactory. Some progress can be reached here by the van der Waals and more advanced density functional methods of description of thermodynamically heterogeneous systems having, however, its limitations in application to the interpretation of experimental data as well. Moreover, both mentioned theories—Gibbs’ and density functional approaches—lead to partly contradicting each other’s results. As shown in preceding papers, by generalizing Gibbs’ approach, existing deficiencies and internal contradictions of these two well-established theories can be removed and a new generally applicable tool for the interpretation of phase formation processes can be developed. In the present analysis, a comparative analysis of the basic assumptions and predictions of the classical and the generalized Gibbs approaches is given. It is shown, in particular, that—interpreted in terms of the generalized Gibbs approach—the critical cluster as determined via the classical Gibbs approach corresponds not to a saddle but to a ridge point of the appropriate thermodynamic potential hypersurface. By this reason, the classical Gibbs approach (involving the classical capillarity approximation) overestimates as a rule the work of critical cluster formation in nucleation theory and, in general, considerably.
\\\\Expert2\\NBO\\Journal of Chemical Physics\\2006, v.124, p.194503.pdf
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2.

Вид документа : Статья из журнала
Шифр издания : 53/S 34
Автор(ы) : Schmelzer J. W. P., Boltachev G. Sh., Baidakov V. G.
Заглавие : Classical and generalized Gibbs' approaches and the work of critical cluster formation in nucleation theory
Место публикации : Journal of Chemical Physics. - 2006. - Vol. 124, № 19. - С. 194503/1-194503/18
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): clusters
Аннотация: In the theoretical interpretation of the kinetics of first-order phase transitions, thermodynamic concepts developed long ago by Gibbs are widely employed giving some basic qualitative insights into these processes. However, from a quantitative point of view, the results of such analysis, based on the classical Gibbs approach and involving in addition the capillarity approximation, are often not satisfactory. Some progress can be reached here by the van der Waals and more advanced density functional methods of description of thermodynamically heterogeneous systems having, however, its limitations in application to the interpretation of experimental data as well. Moreover, both mentioned theories—Gibbs’ and density functional approaches—lead to partly contradicting each other’s results. As shown in preceding papers, by generalizing Gibbs’ approach, existing deficiencies and internal contradictions of these two well-established theories can be removed and a new generally applicable tool for the interpretation of phase formation processes can be developed. In the present analysis, a comparative analysis of the basic assumptions and predictions of the classical and the generalized Gibbs approaches is given. It is shown, in particular, that—interpreted in terms of the generalized Gibbs approach—the critical cluster as determined via the classical Gibbs approach corresponds not to a saddle but to a ridge point of the appropriate thermodynamic potential hypersurface. By this reason, the classical Gibbs approach (involving the classical capillarity approximation) overestimates as a rule the work of critical cluster formation in nucleation theory and, in general, considerably.
\\\\Expert2\\NBO\\Journal of Chemical Physics\\2006, v.124, p.194503.pdf
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3.

Вид документа :
Шифр издания : 53/B 74
Автор(ы) : Boltachev G. Sh., Baidakov V. G., Schmelzer J. W. P.
Заглавие : Is Gibbs' Thermodynamic Theory of Heterogeneous Systems Really Perfect?
Место публикации : Nucleation Theory and Applications. - Berlin: Wiley-VCH Verlag, 2005. - С. 418-446
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): nucleation--gibbs' thermodynamic theory --heterogeneous systems
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4.

Вид документа :
Шифр издания : 53/B 16
Автор(ы) : Baidakov V. G., Schmelzer J. W. P.
Заглавие : Boiling-Up Kinetics of Solutions of Cryogenic Liquids
Место публикации : Nucleation Theory and Applications. - Berlin: Wiley-VCH Verlag, 2005. - С. 126-175
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): nucleation kinetics--diffusion tensor of nuclei--nucleation rates
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5.

Вид документа :
Шифр издания : 53/B 74
Автор(ы) : Boltachev G. Sh., Baidakov V. G., Schmelzer J. W. P.
Заглавие : Is Gibbs' Thermodynamic Theory of Heterogeneous Systems Really Perfect?
Место публикации : Nucleation Theory and Applications. - Berlin: Wiley-VCH Verlag, 2005. - С. 418-446
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): nucleation--gibbs' thermodynamic theory --heterogeneous systems
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6.

Вид документа :
Шифр издания : 53/B 16
Автор(ы) : Baidakov V. G., Schmelzer J. W. P.
Заглавие : Boiling-Up Kinetics of Solutions of Cryogenic Liquids
Место публикации : Nucleation Theory and Applications. - Berlin: Wiley-VCH Verlag, 2005. - С. 126-175
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): nucleation kinetics--diffusion tensor of nuclei--nucleation rates
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7.

Вид документа :
Шифр издания : 53/S 34
Автор(ы) : Schmelzer J. W. P., Baidakov V. G.
Заглавие : Comment on “Multicomponent nucleation: Thermodynamically consistent description of the nucleation work”
Место публикации : Journal of Chemical Physics. - 2004. - Vol.121, №3. - С. 1644-1645
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): thermodynamically consistent--nucleations--critical cluster
Аннотация: In the above cited paper, Kashchiev extends the “thermodynamically consistent” description of nucleation work to phase formation processes in multicomponent systems. It is claimed that this approach is generally applicable widely independent on the kind of phase transformation considered. In contrast to this statement, it is shown in our Comment that Kashchiev’s approach is theoretically not well founded. It contains, in addition, a number of assumptions, which are not generally fulfilled. Because of this his method cannot give, in general, a satisfactory determination of the work of critical cluster formation in nucleation theory. An experimental example is given verifying our
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8.

Вид документа :
Шифр издания : 53/S 34
Автор(ы) : Schmelzer J. W. P., Baidakov V. G.
Заглавие : Comment on “Multicomponent nucleation: Thermodynamically consistent description of the nucleation work”
Место публикации : Journal of Chemical Physics. - 2004. - Vol.121, №3. - С. 1644-1645
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): thermodynamically consistent--nucleations--critical cluster
Аннотация: In the above cited paper, Kashchiev extends the “thermodynamically consistent” description of nucleation work to phase formation processes in multicomponent systems. It is claimed that this approach is generally applicable widely independent on the kind of phase transformation considered. In contrast to this statement, it is shown in our Comment that Kashchiev’s approach is theoretically not well founded. It contains, in addition, a number of assumptions, which are not generally fulfilled. Because of this his method cannot give, in general, a satisfactory determination of the work of critical cluster formation in nucleation theory. An experimental example is given verifying our
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9.

Вид документа :
Шифр издания : 53/S 34
Автор(ы) : Schmelzer J. W. P., Baidakov V. G.
Заглавие : On different possibilities of a thermodynamically consistent determination of the work of critical cluster formation in nucleation theory
Место публикации : Journal of Chemical Physics. - 2003. - Vol.119, №20. - С. 10759-10763
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): thermodynamic properties --clusters--nucleation
Аннотация: In a recent paper [J. Chem. Phys. 118, 1837 (2003)], Kashchiev claimed to have developed a general thermodynamically consistent formula allowing one to describe correctly the work of critical cluster formation in one-component systems for a variety of cases of formation of gaseous, liquid, and solid phases. It is shown that most of the consequences drawn lack any substantiation
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10.

Вид документа :
Шифр издания : 53/B 74
Автор(ы) : Boltachev G. Sh., Schmelzer J. W. P., Baidakov V. G.
Заглавие : First-order curvature corrections to the surface tension of multicomponent systems
Место публикации : Journal of Colloid and Interface Sience. - 2003. - Vol.264, №1. - С. 228-236
ББК : 53
Предметные рубрики: ФИЗИКА
Ключевые слова (''Своб.индексиров.''): surface tension--phase coexistence--multicomponent systems
Аннотация: The dependence of surface tension on curvature is investigated for the case of an equilibrium phase coexistence in multicomponent systems. Employing Gibbs's method of description of heterogeneous systems, an equation is derived to determine the dependence of surface tension on curvature for widely arbitrary paths of variation of the independent thermodynamic parameters. It is supposed hereby merely that the temperature is kept constant and that the variations of the different molar fractions are such that the radius of the dividing surface varies monotonically in dependence on the change of the state parameters of the ambient phase along any of the chosen paths. In the analysis, an approach developed by Blokhuis and Bedeaux for one-component systems is utilized. It relies on the expansion of the surface free energy on curvature of the dividing surface. An equation is derived that connects the first-order correction term in the expansion with the interaction potential of the particles in the multicomponent solution and with the two-particle distribution functions in the planar interfacial layer between the two phases coexisting in equilibrium at planar interfaces. The connection of the first-order curvature correction to the surface tension and the first moment of the pressure tensor at a planar interface is analyzed as well
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